Evidence of nano-galvanic couple formation on in-situ formed nano-aluminum amalgam surfaces for passivation-bypassed water splitting

Reaction of Al metal with water is a well-known technique for large scale production of hydrogen. However, this method suffers from kinetic limitations due to formation of a passivation layer on Al, preventing optimal operations. Using high resolution Scanning Kelvin Probe Force Microscopy (SKPFM), we show the origin of formation of 'nano-galvanic couple' on in situ formed nano-aluminum amalgam surfaces in a water splitting system; passivation based limitations are completely bypassed in this approach. Furthermore, they offer an opportunity to beneficiate and recover mercury in contaminated water. The nano-galvanic corrosion due to substantial lateral variation in surface contact potential is responsible for the observed high throughput of hydrogen production (720 mL/min per 0.5 g Al salt). It may be noted that this process fares better than in situ prepared nano-Al based hydrogen production, wherein 600 mL/min of hydrogen is obtained for 0.5 g Al salt. Investigations using Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) provide evidence for passivation-bypassed hydrolysis and favourable kinetics for in situ derived nano-AlHg hydrolytic agents (when compared to nano-Al). This study, to the best of our knowledge, reports the first direct proof of nano-galvanic couple formation on in-situ prepared nanoaluminum amalgam surface; paving a direct way to overcome the long standing passivation problem in Al hydrolysis. It is found that the hydrogen production rate and standard deviation (SD) of the contact potential of nanoaluminum amalgam are directly related to the rate of addition of the reducing agent, offering an opportunity for kinetic control for the in situ hydrolytic process.     

Conditional and composite temporal CSPs

Constraint Satisfaction Problems (CSPs) have been widely used to solve combinatorial problems. In order to deal with dynamic CSPs where the information regarding any possible change is known a priori and can thus be enumerated beforehand, conditional constraints and composite variables have been studied in the past decade. Indeed, these two concepts allow the addition of variables and their related constraints in a dynamic manner during the resolution process. More precisely, a conditional constraint restricts the participation of a variable in a feasible scenario while a composite variable allows us to express a disjunction of variables where only one will be added to the problem to solve. In order to deal with a wide variety of real life applications under temporal constraints, we present in this paper a unique temporal CSP framework including numeric and symbolic temporal information, conditional constraints and composite variables. We call this model, a Conditional and Composite Temporal CSP (or CCTCSP). To solve the CCTCSP we propose two methods respectively based on Stochastic Local Search (SLS) and constraint propagation. In order to assess the efficiency in time of the solving methods we propose, experimental tests have been conducted on randomly generated CCTCSPs. The results demonstrate the superiority of a variant of the Maintaining Arc Consistency (MAC) technique (that we call MAX+) over the other constraint propagation strategies, Forward Checking (FC) and its variants, for both consistent and inconsistent problems. It has also been shown that, in the case of consistent problems, MAC+ outperforms the SLS method Min Conflict Random Walk (MCRW) for highly constrained CCTCSPs while both methods have comparable time performance for under and middle constrained problems. MCRW is, however, the method of choice for highly constrained CCTCSPs if we decide to trade search time for the quality of the solution returned (number of solved constraints).     

Development of Weld Metal Microstructures in Pulsed Laser Welding of Duplex Stainless Steel

The microstructure of the weld metal of a duplex stainless steel made with Nd:YAG pulsed laser is investigated at different travel speeds and pulse frequencies. In terms of the solidification pattern, the weld microstructure is shown to be composed of two distinct zones. The presence of two competing heat transfer channels to the relatively cooler base metal and the relatively hotter previous weld spot is proposed to develop two zones. At high overlapping factors, an array of continuous axial grains at the weld centerline is formed. At low overlapping factors, in the zone of higher cooling rate, a higher percentage of ferrite is transformed to austenite. This is shown to be because with extreme cooling rates involved in pulsed laser welding with low overlapping, the ferrite-to-austenite transformation can be limited only to the grain boundaries.     

Nitrate reduction in a simulated free-water surface wetland system

The feasibility of using a constructed wetland for treatment of nitrate-contaminated groundwater resulting from the land application of biosolids was investigated for a site in the southeastern United States. Biosolids degradation led to the release of ammonia, which upon oxidation resulted in nitrate concentrations in the upper aquifer in the range of 65-400 mg N/L. A laboratory-scale system was constructed in support of a pilot-scale project to investigate the effect of temperature, hydraulic retention time (HRT) and nitrate and carbon loading on denitrification using soil and groundwater from the biosolids application site. The maximum specific reduction rates (MSRR), measured in batch assays conducted with an open to the atmosphere reactor at four initial nitrate concentrations from 70 to 400 mg N/L, showed that the nitrate reduction rate was not affected by the initial nitrate concentration. The MSRR values at 22 °C for nitrate and nitrite were 1.2 ± 0.2 and 0.7 ± 0.1 mg N/mg VSS_COD-day, respectively. MSRR values were also measured at 5, 10, 15 and 22 °C and the temperature coefficient for nitrate reduction was estimated at 1.13. Based on the performance of laboratory-scale continuous-flow reactors and model simulations, wetland performance can be maintained at high nitrogen removal efficiency (>90%) with an HRT of 3 days or higher and at temperature values as low as 5 °C, as long as there is sufficient biodegradable carbon available to achieve complete denitrification. The results of this study show that based on the climate in the southeastern United States, a constructed wetland can be used for the treatment of nitrate-contaminated groundwater to low, acceptable nitrate levels.     

Cathodic electrodeposition of Y(OH)3 and Y2O3 nanostructures from chloride bath. Part II: Effect of the bath temperature on the crystal structure,composition and morphology

Ultra-fine nanoparticles, mono-dispersed nanospheres and nanorods of Y(OH)₃ and Y₂O₃ were successfully prepared via electrodeposition from chloride bath at different temperatures of 10, 25, 40 and 80 °C followed by heat-treatments at 600 °C in dry air atmosphere. Thermal behavior of the hydroxide samples was investigated by differential scanning calorimetry (DSC) and thermogravimetric (TG) analysis. The structural and morphological characteristics of the products were determined by X-ray diffraction (XRD), FT-IR, scanning and transmission electron microscopy (SEM and TEM). Effects of bath temperature on the mechanism of base electrogeneration and deposit formation on the cathode surface were proposed and discussed. The results showed that the crystal structure, composition and morphology of the products are mainly affected by the temperature of electrodeposition bath.     

The Ablation and Oxidation Behaviors of SiC Coatings on Graphite Prepared by Slurry Sintering and Pack Cementation

SiC coatings were generated on graphite using slurry sintering (SS) and pack cementation (PC). The samples’ ablation features were assessed by an oxyacetylene torch. The rates of mass ablation of the PC–SiC and SS–SiC coatings were approximated 2.17?×?10^?3 and 9.52?×?10^?3 g s^?1, respectively, decreased by 84.1 and 29.6% compared to the uncoated samples. It was mainly attributed to the formation of a SiO₂ layer on the surface. The continuous SiO₂ molten film formed via the PC–SiC oxidation generates a sealing mechanism which can be an obstacle against the oxygen diffusion and hinder more ablation. This is while discontinuous SiO₂ film formed from the thin SS–SiC cannot protect the graphite effectively. The non-isothermal oxidation test shows that without the SiC coating, the sample weight is lost largely from 25 to 1500 °C, and its weight loss was 2.2% after the TGA. However, after coating, the samples possessed excellent oxidation protection and weight losses of SS–SiC and PC–SiC coatings are down to 1.3 and 0.6%, respectively. The more oxidation of the graphite substrate occurred due to the formation of macrocracks in the coating during the TGA and also the formation of holes on SiO₂ glass layer owing to release of CO or CO₂.     

Synthesis and characterization of new polyurethanes: influence of monomer composition

Different polyurethanes (PU) were synthesized from polycaprolactone diol, 1.6-hexamethylene diisocyanate and bis(2-hydroxyethyl)terephthalate, using a two- and one-step methods providing regular and random distributions of starting monomers in the polyurethane chains. Even with an identical molar monomer composition, the properties of obtained PU are different depending on the method of synthesis. The chemical structure of PU was characterized by ¹H and ¹³C NMR spectroscopy, as well as by FTIR and UV–Visible spectroscopy. The thermo-mechanical and hydrophilic properties of synthesized PU were also studied demonstrating the influence of aromatic ring in the macromolecular chain.     

Vapour side corrosion in a ME desalination plant at Jebel Dhana

Jebel Dhana, from the Abu Dhabi Water and Electricity Authority (ADWEA), operates two 2 MGD multi-effect thermo-compression distillers commissioned in 1996. Tube failures were first reported approximately 16 months after commissioning. The initial tube failures were from the upper rows, but more recent failures were apparently randomly distributed throughout the tube bundle. Ten tubes were removed and their corrosion morphology was examined macroscopically and microscopically. The corrosion products were analysed by X-ray, EDAX, and EPMA techniques. The copper nickel alloy tubes were found to have suffered from vapour side corrosion; however, there was no sign of any copper oxide deposition, as has often been seen in failed tubes from MSF distillers. The failures took two forms: corrosion fatigue cracking, and pitting corrosion. The corrosion fatigue was in the form of a circumferential crack at a flat portion of the tube in the centre of a tube span. It was believed that the flat surface had developed as a result of fretting against a neighbouring tube, and had been worn away to the point of failure. Unfortunately, the position of the tubes in the tube bundle had not been identified during their removal, but it is suspected that the damaged tube had been in the top row, with the flattened portion directly below one of the two vapour inlet pipes. The other tubes sampled showed pitting corrosion. Some of the pitting had perforated the tube walls whilst others showed pitting on the outer surface only. Some of the pits contained corrosion products whilst others were free of them. This pitting corrosion is attributed to the formation of carbonic acid in the presence of oxygen (air). A weak acid is formed due to the dissolution of CO₂ in the condensing water vapour. The gas concentration varies within the tube bundle, due to the vapour phase, allowing the gas concentration to increase in specific areas of the tube bundle, causing the non-uniformity of attack. There was no immediate tie-up between the pitting corrosion and the two steam inlet pipes due to the unknown position of the sampled tubes within the tube bundle. It is recommended that the oxygen level be reduced by ensuring that the distiller vessels are as air-tight as possible, thus reducing the tendency towards pitting corrosion.